267665-95-2

Upstream product

• 591-50-4 iodobenzene 
• 77-76-9 2,2-dimethoxy-propane 
• 4688-38-4 (2R,3S)-1,2-O-isopropylidene-4-pentyne-1,2,3-triol 
• 15186-48-8 2,3-isopropylidene-glyceraldehyde 
• 22323-82-6 (S)-(+)-(2,2-dimethyl-[1,3]dioxolan-4-yl)methanol 
• 889862-52-6 trans-2-benzylsulfonyl-1-(2,2-dimethyl-1,3-dioxolan-4-yl)ethene 
• 889862-53-7 trans-(2R,3R)-2-benzylsulfonyl-3-(2,2-dimethyl-1,3-dioxolan-4-yl)oxirane 
• 208114-17-4 (1S,5'R)-1-(2',2'-dimethyl-[1',3']dioxolan-4-yl)-3-phenyl-prop-2-yn-ol 

Downstream Products

• 208048-43-5 trans-(1S,5'R)-1-diazoacetic acid 1-(2',2'-dimethyl-[1',3']dioxolane-4'-yl)-3-phenyl-prop-2-enyl ester 
• 137616-53-6 (2R,3S)-trans-5-phenyl-4-penten-1,2,3-triol 

Relevant academic research and scientific papers

Diastereodivergent Synthesis of 2-Ene-1,4-hydroxy Sulfides from 2-Sulfinyl Dienes via Tandem Sulfa-Michael/Sulfoxide-Sulfenate Rearrangement

The highly diastereoselective sulfa-Michael addition of thiolates to enantiopure 2-sulfinyl dienes leads to anti or syn 2-ene-1,4-hydroxy sulfides in good yields and selectivities dependent on the reaction conditions in a diastereodivergent process. Synthetic applications of these enantiopure hydroxy sulfides by subsequent sigmatropic rearrangements have been outlined.

The epoxy-Ramberg-Baecklund reaction (ERBR): A sulfone-based method for the synthesis of allylic alcohols

The epoxy-Ramberg-Baecklund reaction (ERBR) is outlined, in which α,β-epoxy sulfones are converted into a range of mono-, di- and tri-substituted allylic alcohols, on treatment with base. Modification of this method enabled the preparation of enantio-enriched allylic alcohols following the diastereoselective epoxidation of enantio-enriched vinyl sulfones that were accessed efficiently from the chiral pool. The scope, optimisation and limitations of the ERBR as a method for the preparation of allylic alcohols are discussed. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

Applications of intramolecular cyclopropanations of chiral secondary allylic diazoacetates

The diastereomeric secondary allylic diazoacetates 6a,b and 8a,b, which were readily prepared from the common intermediate 4, were cyclized in the presence of the achiral catalyst Cu(TBS)2 to furnish mixtures of the adducts 9a,b/10a,b and 12a,b/13a,b, respectively; in these cyclizations, the diastereoselectivity of the reaction was substrate controlled. When 6a,b and 8a,b were cyclized in the presence of the chiral catalysts Rh2[(5S)-MEPY]4 or Rh2[(5A)-MEPY]4, the substrate-based selectivity could be reversed if the chirality of the substrate and catalyst were matched. The advantages associated with the use of chiral catalysts to effect the diastereoselective cyclization of chiral allylic diazoacetates were demonstrated by the synthesis of 25, which comprises the cyclopropane subunit found in the diterpene ingol B (14).

Diastereodifferentiation in intramolecular cyclopropanations of chiral secondary allylic diazoacetates

Intramolecular cyclopropanations of diastereomeric, secondary allylic diazoacetates were carried out in the presence of an achiral copper catalyst, Cu(TBS)2, and the chiral rhodium catalysts Rh2[5(S)-MEPY]4 and Rh2[5(R)- MEPY]4 to give diastereomeric cyclopropyl lactones in ratios that varied with catalyst and stereochemistry of the starting material.